CN115612059B - Bio-based sponge - Google Patents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/6795—Unsaturated polyethers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
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- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
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Abstract
The invention relates to the field of sponges, in particular to a biological-based sponge which comprises the following components in parts by weight: 100 parts of castor oil polyether polyol, 29.7-35.3 parts of TDI80,0.6-0.8 part of common soft foam silicone oil, 0.32-0.4 part of amine catalyst A33,0.19-0.24 part of tin catalyst T9,2-3 parts of water and 1.7-2.2 parts of reinforcing agent. The bio-based sponge is a bio-based polyurethane series sponge synthesized by taking bio-based castor oil-based polyether polyol as polyol and TDI80 as diisocyanate. The sponge has the greatest characteristics that the castor oil base group containing the biological base structure is used, the environment-friendly effect is better, and compared with the biological base series in the current market, the prepared sponge has better mechanical property, elasticity and comfortableness and bacteriostasis.
Description
Technical Field
The invention relates to the field of sponges, in particular to a biological-based sponge.
Background
Sponges are quite common in living applications, such as sofas, chairs, mattresses and shoes, where a large amount of sponges are present. The soft and comfortable experience is provided for people, so that the soft and comfortable soft tea is widely used in different fields by people. The sponge commonly used by people is made of wood cellulose fiber or foamed plastic polymer. In addition, there are also natural sponges made of sponges, and synthetic sponges made of three other materials, respectively, low density polyether (non-absorbent sponges), polyvinyl alcohol (super absorbent materials, no obvious pores) and polyester sponges.
In the prior art, soft sponge is often selected as filling sponge in mattresses and pillows, but the prior sponge for filling has the defects that: the prior sponge has few sponges which use polyol reaction based on bio-based synthesis, and meanwhile, the prior sponge has poor bacteriostasis.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a biological-based sponge.
The aim of the invention is realized by adopting the following technical scheme:
in a first aspect, the invention provides a bio-based sponge, which comprises the following components in parts by weight:
100 parts of castor oil polyether polyol, 29.7-35.3 parts of TDI80,0.6-0.8 part of common soft foam silicone oil, 0.32-0.4 part of amine catalyst A33,0.19-0.24 part of tin catalyst T9,2-3 parts of water and 1.7-2.2 parts of reinforcing agent.
Preferably, the biological-based sponge comprises the following components in parts by weight:
100 parts of castor oil polyether polyol, 33.6 parts of TDI80,0.7 part of common soft foam silicone oil, 0.36 part of amine catalyst A33,0.22 part of tin catalyst T9,2.5 parts of water and 1.9 parts of reinforcing agent.
Preferably, the castor oil polyether polyol is a polyether polyol obtained by ring-opening polymerization of propylene oxide under the action of a bimetallic catalyst DMC by taking renewable resource castor oil as a starter.
Preferably, the castor oil polyether polyol is prepared by the following steps:
mixing castor oil and a bimetallic catalyst DMC into a reaction vessel, heating to 105 ℃, decompressing and dehydrating, introducing nitrogen as a protective gas, firstly adding propylene oxide into the reaction vessel, controlling the pressure in the reaction vessel to be 0.3MPa, and keeping for 20-30min; then heating to 160-200 ℃, adding propylene oxide for the second time, reacting for 2-4 hours at a constant temperature, discharging under reduced pressure, and removing impurities to obtain castor oil polyether polyol;
wherein the adding amount of the bimetallic catalyst DMC is 1% -2% of the mass of castor oil, and the mass ratio of the castor oil, the propylene oxide added for the first time and the propylene oxide added for the second time is 2.1-2.5:0.4:0.6.
Preferably, the TDI80 is a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate; wherein the mass ratio of the 2, 4-toluene diisocyanate is 80%.
Preferably, the model of the common soft foam silicone oil is any one of silicone oil L595, silicone oil L633 and silicone oil L668.
Preferably, the amine catalyst a33 is a dipropylene glycol solution of triethylenediamine; wherein the mass fraction of the triethylene diamine is 33%, and the mass fraction of the dipropylene glycol is 67%.
Preferably, the tin catalyst T9 is stannous octoate catalyst, wherein the tin content is more than or equal to 28.0wt%.
Preferably, the reinforcing agent is a polycycloalkene carbonate/polylactide modified zeolite (PLC/PLA-CS).
Preferably, the preparation method of the polycycloalkene carbonate comprises the following steps:
weighing limonene epoxide and zinc complex catalyst, mixing into a reaction container, sealing the reaction container, vacuumizing to remove air, then introducing carbon dioxide until the pressure reaches 3-5MPa, stirring and reacting for at least 48 hours at room temperature, and removing impurities and drying the obtained product to obtain the poly (limonene carbonate);
wherein the addition amount of the zinc complex catalyst is 0.5-1% of the mass of the limonene epoxide.
Preferably, the preparation method of the polycycloalkene carbonate/polylactide modified zeolite comprises the following steps:
s1, weighing zeolite particles, sintering for 20-30min at 300-500 ℃, dispersing in absolute ethyl alcohol after cooling, adding vinyl triethoxysilane for ultrasonic treatment for 0.5-1h, filtering out the particles, and drying to obtain activated zeolite particles;
wherein the particle size of the zeolite particles is 1 mu m, and the mass ratio of the zeolite particles, the vinyl triethoxysilane and the absolute ethyl alcohol is 1:0.1-0.3:10-20;
s2, weighing lactide and activated zeolite particles, mixing in DMF, introducing nitrogen as a shielding gas, and uniformly stirring and mixing to form a lactide/zeolite mixed solution;
wherein the mass ratio of the activated zeolite particles to the lactide to the DMF is 1:1.2-1.4:10-20;
s3, sequentially adding a poly (limonene carbonate) and a zinc complex catalyst into the lactide/zeolite mixed solution, stirring and mixing at 140-160 ℃ for reaction for 24-48 hours, and removing the solvent under reduced pressure after the reaction is finished to obtain the poly (limonene carbonate)/poly (lactide) modified zeolite;
wherein the mass ratio of the mixed solution of the poly (limonene carbonate) and the lactide/zeolite is 1.5-1.7:10-20, and the addition amount of the zinc complex catalyst is 1% -2% of the mass of the poly (limonene carbonate).
In a second aspect, the present invention provides a method for preparing a bio-based sponge, comprising the steps of:
(1) Sequentially weighing castor oil polyether polyol, common soft foam silicone oil, an amine catalyst A33, a tin catalyst T9, an enhancer and water according to the weight parts of the components, mixing in a reaction container, and uniformly stirring and mixing to form a mixed reaction solution;
(2) Adding TDI80 into the mixed reaction liquid, stirring for reaction, pouring into a mould, curing and cooling to obtain the bio-based sponge.
Preferably, in the formation process of the mixed reaction liquid, the stirring speed is 800-1200r/min, the stirring time is 5-10min, and the stirring temperature is 20-30 ℃.
Preferably, in the process of adding the TDI80 into the mixed reaction solution, after the TDI80 is completely added, stirring rapidly, wherein the stirring speed is 1500-2000r/min, the stirring time is 6-10s, and the stirring temperature is 20-30 ℃; the mold is preheated in an oven at 55-65 ℃ in advance, poured into the mold, treated for 6-10min, demolded and cooled to normal temperature.
The beneficial effects of the invention are as follows:
1. the invention designs a bio-based sponge, which is a bio-based polyurethane series sponge synthesized by taking bio-based castor oil-based polyether polyol as polyol and TDI80 as diisocyanate. The sponge has the greatest characteristics that the castor oil base group containing the biological base structure is used, the environment-friendly effect is better, and compared with the biological base series in the current market, the prepared sponge has better mechanical property, elasticity and comfortableness and bacteriostasis.
2. Soft foam silicone oil is added into the raw materials of the bio-based sponge, so that the sponge has uniform air holes and plays a role in stabilizing the cells. The added reinforcing agent is obtained by taking zeolite as a matrix and modifying the surface of the matrix, and comprises the steps of sintering the zeolite at high temperature, dredging pore channels and increasing the surface area, treating the surface of the zeolite by using a silane coupling agent to activate the surface of the zeolite, blending and modifying the zeolite with lactide to obtain lactide/zeolite mixed solution, and finally reacting and combining the lactide/zeolite mixed solution with the prepared poly (limonene carbonate) to obtain the reinforcing agent. The reinforcing agent has better performance and compatibility than the traditional zeolite.
3. In the invention, after lactide/zeolite and the poly (limonene carbonate) are fully contacted, the temperature is raised for reaction, lactide is subjected to ring opening and then is crosslinked and polymerized with the poly (limonene carbonate) to obtain a segmented copolymer which is coated on the surface of the zeolite, and the obtained product structure not only has a limonene group, but also has a poly (lactide) block. The prepared reinforcing agent is added into the biological-based sponge as an additive modifier, so that the mechanical property of the sponge is improved better, the toughness and the supportability are improved, and the biological-based sponge has certain antibacterial property.
Detailed Description
The technical features, objects and advantages of the present invention will be more clearly understood from the following detailed description of the technical aspects of the present invention, but should not be construed as limiting the scope of the invention.
In the invention, the saponification value of castor oil is 176-182mgKOH/g, density: 0.965-0.970g/cm 3 。
CAS number of propylene oxide: 75-56-9, purity not less than 99%, molecular formula: c (C) 3 H 6 O。
The lactide is D, L-lactide, the purity is more than or equal to 99.5 percent, and the molecular formula is as follows: c (C) 6 H 8 O 4 。
The bimetallic catalyst DMC is purchased from Shanghai Qik fluorosilicone materials Co., ltd, and the effective component is more than or equal to 95%.
The zinc complex catalyst can be purchased directly from the market or synthesized by itself, and the synthesis method is prepared by referring to patent document CN107501535B of Changzhou university (the invention is synthesized by itself by using the method of example 1 of the patent document of Changzhou university).
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
The invention will be further described with reference to the following examples.
Example 1
The biological-based sponge comprises the following components in parts by weight:
100 parts of castor oil polyether polyol, 33.6 parts of TDI80,0.7 part of common soft foam silicone oil, 0.36 part of amine catalyst A33,0.22 part of tin catalyst T9,2.5 parts of water and 1.9 parts of reinforcing agent.
The castor oil polyether polyol is prepared by ring-opening polymerization of propylene oxide under the action of a bimetallic catalyst DMC by taking renewable resource castor oil as an initiator. The preparation process of the castor oil polyether polyol comprises the following steps:
mixing castor oil and a bimetallic catalyst DMC into a reaction vessel, heating to 105 ℃, decompressing and dehydrating, introducing nitrogen as a protective gas, firstly adding propylene oxide into the reaction vessel, controlling the pressure in the reaction vessel to be 0.3MPa, and keeping for 25min; then heating to 180 ℃, adding propylene oxide for the second time, carrying out heat preservation reaction for 3 hours, discharging under reduced pressure, and removing impurities to obtain castor oil polyether polyol; wherein the adding amount of the bimetallic catalyst DMC is 1.5% of the mass of castor oil, and the mass ratio of the castor oil, the propylene oxide added for the first time and the propylene oxide added for the second time is 2.3:0.4:0.6.
Wherein TDI80 is a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate; wherein the mass ratio of the 2, 4-toluene diisocyanate is 80%; the model of the common soft foam silicone oil is silicone oil L595; amine catalyst a33 is a dipropylene glycol solution of triethylenediamine; wherein, the mass fraction of the triethylene diamine is 33 percent, and the mass fraction of the dipropylene glycol is 67 percent; tin catalyst T9 is stannous octoate catalyst, wherein the tin content is more than or equal to 28.0wt%.
Wherein the reinforcing agent is a poly (limonene) carbonate/poly (lactide) modified zeolite (PLC/PLA-CS).
(1) The preparation method of the polycycloalkene carbonate comprises the following steps:
weighing limonene epoxide and zinc complex catalyst, mixing into a reaction container, sealing the reaction container, vacuumizing to remove air, then introducing carbon dioxide until the pressure reaches 4MPa, stirring and reacting for at least 48 hours at room temperature, and removing impurities and drying the obtained product to obtain the poly (limonene carbonate); wherein the addition amount of the zinc complex catalyst is 0.5 percent of the mass of the limonene epoxide.
(2) The preparation method of the polycyclopentadiene carbonate/polylactide modified zeolite comprises the following steps:
s1, weighing zeolite particles, sintering for 25min at 400 ℃, dispersing in absolute ethyl alcohol after cooling, adding vinyl triethoxysilane for ultrasonic treatment for 1h, filtering out the particles, and drying to obtain activated zeolite particles;
wherein the particle size of the zeolite particles is 1 mu m, and the mass ratio of the zeolite particles, the vinyl triethoxysilane and the absolute ethyl alcohol is 1:0.2:15;
s2, weighing lactide and activated zeolite particles, mixing in DMF, introducing nitrogen as a shielding gas, and uniformly stirring and mixing to form a lactide/zeolite mixed solution;
wherein the mass ratio of the activated zeolite particles to the lactide to the DMF is 1:1.3:15;
s3, sequentially adding a poly (limonene) carbonate and a zinc complex catalyst into the mixed solution of the lactide/zeolite, stirring and mixing at 150 ℃ for reaction for 36 hours, and removing the solvent under reduced pressure after the reaction is finished to obtain a poly (limonene) carbonate/poly (lactide) modified zeolite (PLC/PLA-CS);
wherein the mass ratio of the mixed liquid of the poly (limonene carbonate) and the lactide/zeolite is 1.6:15, and the addition amount of the zinc complex catalyst is 1.5 percent of the mass of the poly (limonene carbonate).
The preparation method of the biological-based sponge comprises the following steps:
(1) Sequentially weighing castor oil polyether polyol, common soft foam silicone oil, an amine catalyst A33, a tin catalyst T9, an enhancer and water according to the weight parts of the components, mixing in a reaction vessel, stirring uniformly at a stirring speed of 800r/min for 10min and at a stirring temperature of 20 ℃ to form a mixed reaction solution;
(2) Adding TDI80 into the mixed reaction liquid, rapidly stirring after the TDI80 is completely added, wherein the stirring speed is 1500r/min, the stirring time is 8s, the stirring temperature is 30 ℃, pouring into a mould preheated by an oven at 60 ℃ in advance, processing for 8min, demoulding, and cooling to normal temperature to obtain the bio-based sponge.
Example 2
The biological-based sponge comprises the following components in parts by weight:
100 parts of castor oil polyether polyol, 29.7 parts of TDI80,0.6 part of common soft foam silicone oil, 0.32 part of amine catalyst A33,0.19 part of tin catalyst T9,2 parts of water and 1.7 parts of reinforcing agent.
The castor oil polyether polyol is prepared by ring-opening polymerization of propylene oxide under the action of a bimetallic catalyst DMC by taking renewable resource castor oil as an initiator. The preparation process of the castor oil polyether polyol comprises the following steps:
mixing castor oil and a bimetallic catalyst DMC into a reaction vessel, heating to 105 ℃, decompressing and dehydrating, introducing nitrogen as a protective gas, firstly adding propylene oxide into the reaction vessel, controlling the pressure in the reaction vessel to be 0.3MPa, and keeping for 20min; then heating to 200 ℃, adding propylene oxide for the second time, carrying out heat preservation reaction for 2 hours, discharging under reduced pressure, and removing impurities to obtain castor oil polyether polyol; wherein the adding amount of the bimetallic catalyst DMC is 1% of the mass of castor oil, and the mass ratio of the castor oil, the propylene oxide added for the first time and the propylene oxide added for the second time is 2.1:0.4:0.6.
Wherein TDI80 is a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate; wherein the mass ratio of the 2, 4-toluene diisocyanate is 80%; the model of the common soft foam silicone oil is silicone oil L633; amine catalyst a33 is a dipropylene glycol solution of triethylenediamine; wherein, the mass fraction of the triethylene diamine is 33 percent, and the mass fraction of the dipropylene glycol is 67 percent; tin catalyst T9 is stannous octoate catalyst, wherein the tin content is more than or equal to 28.0wt%.
Wherein the reinforcing agent is a poly (limonene) carbonate/poly (lactide) modified zeolite (PLC/PLA-CS).
(1) The preparation method of the polycycloalkene carbonate comprises the following steps:
weighing limonene epoxide and zinc complex catalyst, mixing into a reaction container, sealing the reaction container, vacuumizing to remove air, then introducing carbon dioxide until the pressure reaches 3MPa, stirring and reacting for at least 48 hours at room temperature, and removing impurities and drying the obtained product to obtain the poly (limonene carbonate); wherein the addition amount of the zinc complex catalyst is 0.5 percent of the mass of the limonene epoxide.
(2) The preparation method of the polycyclopentadiene carbonate/polylactide modified zeolite comprises the following steps:
s1, weighing zeolite particles, sintering for 20min at 300 ℃, dispersing in absolute ethyl alcohol after cooling, adding vinyl triethoxysilane for ultrasonic treatment for 0.5h, filtering out the particles, and drying to obtain activated zeolite particles;
wherein the particle size of the zeolite particles is 1 μm, and the mass ratio of the zeolite particles, the vinyl triethoxysilane and the absolute ethyl alcohol is 1:0.1:10;
s2, weighing lactide and activated zeolite particles, mixing in DMF, introducing nitrogen as a shielding gas, and uniformly stirring and mixing to form a lactide/zeolite mixed solution;
wherein the mass ratio of the activated zeolite particles to the lactide to the DMF is 1:1.2:10;
s3, sequentially adding a poly (limonene carbonate) and a zinc complex catalyst into the mixed solution of the lactide/zeolite, stirring and mixing at 140 ℃ for reaction for 24 hours, and removing the solvent under reduced pressure after the reaction is finished to obtain the poly (limonene carbonate)/poly (lactide) modified zeolite;
wherein the mass ratio of the mixed liquid of the poly (limonene carbonate) and the lactide/zeolite is 1.5:10, and the addition amount of the zinc complex catalyst is 1% of the mass of the poly (limonene carbonate).
The preparation method of the biological-based sponge comprises the following steps:
(1) Sequentially weighing castor oil polyether polyol, common soft foam silicone oil, an amine catalyst A33, a tin catalyst T9, an enhancer and water according to the weight parts of the components, mixing in a reaction vessel, stirring uniformly at a stirring speed of 800r/min for 10min and at a stirring temperature of 20 ℃ to form a mixed reaction solution;
(2) Adding TDI80 into the mixed reaction liquid, rapidly stirring after the TDI80 is completely added, wherein the stirring speed is 1500r/min, the stirring time is 10s, the stirring temperature is 20 ℃, pouring into a mold preheated by an oven at 55 ℃ in advance, treating for 10min, demoulding, and cooling to normal temperature to obtain the bio-based sponge.
Example 3
The biological-based sponge comprises the following components in parts by weight:
100 parts of castor oil polyether polyol, 35.3 parts of TDI80,0.8 part of common soft foam silicone oil, 0.4 part of amine catalyst A33,0.24 part of tin catalyst T9,3 parts of water and 2.2 parts of reinforcing agent.
The castor oil polyether polyol is prepared by ring-opening polymerization of propylene oxide under the action of a bimetallic catalyst DMC by taking renewable resource castor oil as an initiator. The preparation process of the castor oil polyether polyol comprises the following steps:
mixing castor oil and a bimetallic catalyst DMC into a reaction vessel, heating to 105 ℃, decompressing and dehydrating, introducing nitrogen as a protective gas, firstly adding propylene oxide into the reaction vessel, controlling the pressure in the reaction vessel to be 0.3MPa, and keeping for 30min; then heating to 160 ℃, adding propylene oxide for the second time, carrying out heat preservation reaction for 4 hours, discharging under reduced pressure, and removing impurities to obtain castor oil polyether polyol; wherein the adding amount of the bimetallic catalyst DMC is 2% of the mass of castor oil, and the mass ratio of the castor oil, the propylene oxide added for the first time and the propylene oxide added for the second time is 2.5:0.4:0.6.
Wherein TDI80 is a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate; wherein the mass ratio of the 2, 4-toluene diisocyanate is 80%; the model of the common soft foam silicone oil is silicone oil L668; amine catalyst a33 is a dipropylene glycol solution of triethylenediamine; wherein, the mass fraction of the triethylene diamine is 33 percent, and the mass fraction of the dipropylene glycol is 67 percent; tin catalyst T9 is stannous octoate catalyst, wherein the tin content is more than or equal to 28.0wt%.
Wherein the reinforcing agent is a poly (limonene) carbonate/poly (lactide) modified zeolite (PLC/PLA-CS).
(1) The preparation method of the polycycloalkene carbonate comprises the following steps:
weighing limonene epoxide and zinc complex catalyst, mixing into a reaction container, sealing the reaction container, vacuumizing to remove air, then introducing carbon dioxide until the pressure reaches 5MPa, stirring and reacting for at least 48 hours at room temperature, and removing impurities and drying the obtained product to obtain the poly (limonene carbonate); wherein, the addition amount of the zinc complex catalyst is 1 percent of the mass of the limonene epoxide.
(2) The preparation method of the polycyclopentadiene carbonate/polylactide modified zeolite comprises the following steps:
s1, weighing zeolite particles, sintering for 20min at 500 ℃, dispersing in absolute ethyl alcohol after cooling, adding vinyl triethoxysilane for ultrasonic treatment for 1h, filtering out the particles, and drying to obtain activated zeolite particles;
wherein the particle size of the zeolite particles is 1 mu m, and the mass ratio of the zeolite particles, the vinyl triethoxysilane and the absolute ethyl alcohol is 1:0.3:20;
s2, weighing lactide and activated zeolite particles, mixing in DMF, introducing nitrogen as a shielding gas, and uniformly stirring and mixing to form a lactide/zeolite mixed solution;
wherein the mass ratio of the activated zeolite particles to the lactide to the DMF is 1:1.4:20;
s3, sequentially adding a poly (limonene carbonate) and a zinc complex catalyst into the mixed solution of the lactide/zeolite, stirring and mixing at 160 ℃ for reaction for 48 hours, and removing the solvent under reduced pressure after the reaction is finished to obtain the poly (limonene carbonate)/poly (lactide) modified zeolite;
wherein the mass ratio of the mixed liquid of the poly (limonene carbonate) and the lactide/zeolite is 1.7:20, and the addition amount of the zinc complex catalyst is 2% of the mass of the poly (limonene carbonate).
The preparation method of the biological-based sponge comprises the following steps:
(1) Sequentially weighing castor oil polyether polyol, common soft foam silicone oil, an amine catalyst A33, a tin catalyst T9, an enhancer and water according to the weight parts of the components, mixing in a reaction vessel, stirring uniformly at the stirring speed of 1200r/min for 5min and at the stirring temperature of 30 ℃ to form a mixed reaction solution;
(2) Adding TDI80 into the mixed reaction liquid, rapidly stirring after the TDI80 is completely added, wherein the stirring speed is 2000r/min, the stirring time is 6s, the stirring temperature is 30 ℃, pouring into a mold preheated by an oven at 65 ℃ in advance, processing for 6min, demoulding, and cooling to normal temperature to obtain the bio-based sponge.
Comparative example 1
A bio-based sponge differs from example 1 in that: the reinforcing agent is polylactide modified zeolite (PLA-CS).
The coating comprises the following components in parts by weight:
100 parts of castor oil polyether polyol, 33.6 parts of TDI80,0.7 part of common soft foam silicone oil, 0.36 part of amine catalyst A33,0.22 part of tin catalyst T9,2.5 parts of water and 1.9 parts of reinforcing agent.
The preparation method of the polylactide modified zeolite (PLA-CS) comprises the following steps:
s1, weighing zeolite particles, sintering for 25min at 400 ℃, dispersing in absolute ethyl alcohol after cooling, adding vinyl triethoxysilane for ultrasonic treatment for 1h, filtering out the particles, and drying to obtain activated zeolite particles;
wherein the particle size of the zeolite particles is 1 mu m, and the mass ratio of the zeolite particles, the vinyl triethoxysilane and the absolute ethyl alcohol is 1:0.2:15;
s2, weighing lactide and activated zeolite particles, mixing in DMF, introducing nitrogen as a shielding gas, adding a zinc complex catalyst, stirring and mixing at 150 ℃ for reaction for 36 hours, and removing the solvent under reduced pressure after the reaction is finished to form polylactide modified zeolite (PLA-CS);
wherein the mass ratio of the activated zeolite particles to the lactide to the DMF is 1:1.3:15; the amount of zinc complex catalyst added was 1.5% of the mass of lactide.
Comparative example 2
A bio-based sponge differs from example 1 in that: the reinforcing agent is poly (limonene) carbonate (PLC) and is prepared in the same manner as in example 1.
The coating comprises the following components in parts by weight:
100 parts of castor oil polyether polyol, 33.6 parts of TDI80,0.7 part of common soft foam silicone oil, 0.36 part of amine catalyst A33,0.22 part of tin catalyst T9,2.5 parts of water and 1.9 parts of reinforcing agent.
Comparative example 3
A bio-based sponge differs from example 1 in that: the reinforcing agent is a poly (limonene) carbonate modified zeolite (PLC-CS).
The coating comprises the following components in parts by weight:
100 parts of castor oil polyether polyol, 33.6 parts of TDI80,0.7 part of common soft foam silicone oil, 0.36 part of amine catalyst A33,0.22 part of tin catalyst T9,2.5 parts of water and 1.9 parts of reinforcing agent.
The preparation method of the polycycloalkene carbonate modified zeolite (PLC-CS) comprises the following steps:
s1, weighing zeolite particles, sintering for 25min at 400 ℃, dispersing in absolute ethyl alcohol after cooling, adding vinyl triethoxysilane for ultrasonic treatment for 1h, filtering out the particles, and drying to obtain activated zeolite particles;
wherein the particle size of the zeolite particles is 1 mu m, and the mass ratio of the zeolite particles, the vinyl triethoxysilane and the absolute ethyl alcohol is 1:0.2:15;
s2, weighing the poly (limonene carbonate) and mixing the activated zeolite particles in toluene, stirring and mixing uniformly, and removing the solvent under reduced pressure to obtain poly (limonene carbonate) modified zeolite (PLC-CS);
wherein the mass ratio of the zeolite particles after the activation treatment, the polycycloalkene carbonate and the toluene is 1:1.6:15.
In order to more clearly illustrate the invention, the antibacterial anti-mite sponge prepared in the example 1 and the comparative examples 1-3 are compared in performance, the tensile strength is in accordance with the method of GB/T6344, the tearing strength is in accordance with the method of GB/T10808, the deformation recovery rate is in accordance with GB/T6670, and the antibacterial rate is in accordance with the method of GB/T20944.3. The test results are shown in Table 1 below:
TABLE 1 detection results of bio-based sponge material
As can be seen from table 1, example 1 has the best tensile strength, tear strength and deformation recovery, and comparative example 1 may be deficient in that it is not crosslinked with the polycyclopentadiene carbonate, resulting in insufficient strength; the disadvantage of comparative example 2 may be that the strength of the polycyclopentadiene carbonate is improved only to a limited extent, and the performance as a reinforcing agent is not sufficient; while comparative example 3 has better performance than comparative example 2, but is still weaker than example 1 as a whole, probably because of slightly inferior binding to zeolite and insufficient degree of fusion with other materials. In addition, other examples and comparative examples have better antibacterial performance except comparative example 1, which shows that the added poly (limonene carbonate) (PLC) has good antibacterial performance.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The biological-based sponge is characterized by comprising the following components in parts by weight:
100 parts of castor oil polyether polyol, 29.7-35.3 parts of TDI80,0.6-0.8 part of common soft foam silicone oil, 0.32-0.4 part of amine catalyst A33,0.19-0.24 part of tin catalyst T9,2-3 parts of water and 1.7-2.2 parts of reinforcing agent;
the reinforcing agent is a polycycloalkene carbonate/polylactide modified zeolite (PLC/PLA-CS); the preparation method of the poly (limonene) carbonate/poly (lactide) modified zeolite comprises the following steps:
s1, weighing zeolite particles, sintering for 20-30min at 300-500 ℃, dispersing in absolute ethyl alcohol after cooling, adding vinyl triethoxysilane for ultrasonic treatment for 0.5-1h, filtering out the particles, and drying to obtain activated zeolite particles;
wherein the particle size of the zeolite particles is 1 mu m, and the mass ratio of the zeolite particles, the vinyl triethoxysilane and the absolute ethyl alcohol is 1:0.1-0.3:10-20;
s2, weighing lactide and activated zeolite particles, mixing in DMF, introducing nitrogen as a shielding gas, and uniformly stirring and mixing to form a lactide/zeolite mixed solution;
wherein the mass ratio of the activated zeolite particles to the lactide to the DMF is 1:1.2-1.4:10-20;
s3, sequentially adding a poly (limonene carbonate) and a zinc complex catalyst into the lactide/zeolite mixed solution, stirring and mixing at 140-160 ℃ for reaction for 24-48 hours, and removing the solvent under reduced pressure after the reaction is finished to obtain the poly (limonene carbonate)/poly (lactide) modified zeolite;
wherein the mass ratio of the mixed solution of the poly (limonene carbonate) and the lactide/zeolite is 1.5-1.7:10-20, and the addition amount of the zinc complex catalyst is 1% -2% of the mass of the poly (limonene carbonate);
the preparation method of the polycycloalkene carbonate comprises the following steps:
weighing limonene epoxide and zinc complex catalyst, mixing into a reaction container, sealing the reaction container, vacuumizing to remove air, then introducing carbon dioxide until the pressure reaches 3-5MPa, stirring and reacting for at least 48 hours at room temperature, and removing impurities and drying the obtained product to obtain the poly (limonene carbonate);
wherein the addition amount of the zinc complex catalyst is 0.5-1% of the mass of the limonene epoxide.
2. The bio-based sponge according to claim 1, wherein the bio-based sponge comprises the following components in parts by weight:
100 parts of castor oil polyether polyol, 33.6 parts of TDI80,0.7 part of common soft foam silicone oil, 0.36 part of amine catalyst A33,0.22 part of tin catalyst T9,2.5 parts of water and 1.9 parts of reinforcing agent.
3. The bio-based sponge according to claim 1, wherein the castor oil polyether polyol is a polyether polyol obtained by ring-opening polymerization of propylene oxide with castor oil as a starter under the action of a bimetallic catalyst DMC.
4. A bio-based sponge according to claim 3, wherein the castor oil polyether polyol is prepared by the process of:
mixing castor oil and a bimetallic catalyst DMC into a reaction vessel, heating to 105 ℃, decompressing and dehydrating, introducing nitrogen as a protective gas, firstly adding propylene oxide into the reaction vessel, controlling the pressure in the reaction vessel to be 0.3MPa, and keeping for 20-30min; then heating to 160-200 ℃, adding propylene oxide for the second time, reacting for 2-4 hours at a constant temperature, discharging under reduced pressure, and removing impurities to obtain castor oil polyether polyol;
wherein the adding amount of the bimetallic catalyst DMC is 1% -2% of the mass of castor oil, and the mass ratio of the castor oil, the propylene oxide added for the first time and the propylene oxide added for the second time is 2.1-2.5:0.4:0.6.
5. The bio-based sponge of claim 1, wherein TDI80 is a mixture of 2, 4-toluene diisocyanate and 2, 6-toluene diisocyanate; wherein the mass ratio of the 2, 4-toluene diisocyanate is 80%.
6. The bio-based sponge according to claim 1, wherein the type of the common soft foam silicone oil is any one of silicone oil L595, silicone oil L633, silicone oil L668.
7. The bio-based sponge of claim 1, wherein the amine catalyst a33 is a dipropylene glycol solution of triethylenediamine; wherein, the mass fraction of the triethylene diamine is 33 percent, and the mass fraction of the dipropylene glycol is 67 percent; the tin catalyst T9 is stannous octoate catalyst, wherein the tin content is more than or equal to 28.0wt%.
8. A method of preparing a bio-based sponge according to any one of claims 1 to 7, comprising the steps of:
(1) Sequentially weighing castor oil polyether polyol, common soft foam silicone oil, an amine catalyst A33, a tin catalyst T9, an enhancer and water according to the weight parts of the components, mixing in a reaction container, and uniformly stirring and mixing to form a mixed reaction solution;
(2) Adding TDI80 into the mixed reaction liquid, stirring for reaction, pouring into a mould, curing and cooling to obtain the bio-based sponge.
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